Facts and artefacts in attempts to separate racemates with the assistance of ionizing radiation

The paper analyses critically attempts to separate racemates by ionizing radiation processing. The effects are low, and prospects to find a commercially promising system are poor. The basic research on chiral effects of ionizing radiation should be continued, because of fundamental importance.     

Lamellar conglomerates

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Thermoanalytical methods in the study of inorganic thin films

Thermoanalytical (TA) methods are relatively seldom applied for assessing the physical and chemical proeprties of thin films, but they can be used in studies of composition, phase transitions and film—substrate interactions. In the present paper the possibilities of TA methods in thin film studies are reviewed. The thermoanalytical methods considered are the classical TG and DTA/DSC methods but some complementary methods will also be briefly mentioned. The main emphasis is given to true thin films. Details of sample preparation are also given. An important application of TA methods is characterization of precursors for the CVD growth of thin films, and this is also discussed.     

利伐沙班中间体的合成工艺研究

本文以溴苯为起始原料,经Ullmann反应、N-酰基化、吗啉酮环合、芳环硝基化、芳硝基还原、2-噁唑烷酮环合共六步反应制得了利伐沙班的关键中间体,所得目标化合物经质谱、核磁共振氢谱确认,总收率达到44.50%。     

Determination of thyroxine enantiomers in pharmaceutical formulation by high-performance liquid chromatography-mass spectrometry with precolumn derivatization

A sensitive and specific liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) method for the separation and analysis of d- and l-thyroxine was developed using R(−)/S(+)-4-(3-isothiocyanatopyrrolidin-1-yl)-7-(N,N-dimethylaminosulfonyl-2,1,3-benzoxadiazole, [R(−)/S(+)-DBD-PyNCS] as a chiral derivatization reagents. The T₄ derivatives with R(−)-DBD-PyNCS were efficiently separated on a reversed-phase column with water-acetonitrile containing 0.1% formic acid (41:59, v/v) as the eluent and analyzed using ESI-MS with negative selected ion monitoring (SIM) mode. The calibration curves of both the d-T₄ and l-T₄ were linear over the concentration range of 0.13-13 μg/ml. The detection limits (S/N = 3) were 28 ng/ml for d-T₄ and 40 ng/ml for l-T₄, respectively. The relative standard deviations (RSD, n = 5) were less than 3.6% at 1.3 μg/ml for both T₄ enantiomers. The proposed method was applied to the determination of l-T₄ enantiomer in a pharmaceutical formulation.     

Thermal characterization of polyethylene glycols applied in the pharmaceutical technology using differential scanning calorimetry and hot stage microscopy

In the present study, the effect of the molecular weight and thermal treatments on commercial polyethylene glycols (PEG) samples used in the pharmaceutical processing technology, has been analyzed using DSC and HSM. The molecular weight of these polymers range from 1500 to 200000. Thermal investigations on the melting behavior of original PEG samples (as received from the manufacturer) showed only one single melting DSC endotherm effect before 373 K. This fact was associated to the presence of only one type of polymeric chain. Using standard conditions, PEG samples were solidified from the melt at 373 K, either by flash cooling (using liquid nitrogen and an ice bath) and by slow cooling, soaked and by slow cooling at room temperature. They were further studied by DSC. It was found that after cooling, PEG with molecular weight 1500 and 15000 showed DSC thermograms with a single endothermic peak. However, thermograms for PEG 4000 and 6000 produced a splitted melting endotherm. This fact was attributed to the presence of two types of chains, that are the folded and extended chains.Ageing time influences also the shape of the DSC endothermal effects. It was concluded that the endotherms obtained after heating these PEG indicate that the thermal history determine the structure (extended or folded chain type forms) and the degree of crystallinity, as evidenced by changes in heat of fusion values, melting points and structures after crystallization. The relationships between melting enthalpies and melting points, as deduced from DSC diagrams, with molecular weight of the polymers are also presented.     

Enantioseparation of phenotiazines by affinity electrokinetic chromatography using human serum albumin as chiral selector: application to enantiomeric quality control in pharmaceutical formulations

Nowadays, there is a special interest within the pharmaceutical laboratories to develop single enantiomer formulations and consequently a need for analytical methods to determine the enantiomeric purity of drugs. The present paper deals with the enantiomeric separation of promethazine and trimeprazine enantiomers by affinity electrokinetic chromatography (AEKC)-partial filling technique using human serum albumin (HSA) as chiral selector. A multivariate optimization of the most critical experimental variables in enantioresolution, running pH, HSA concentration and plug length, is carried out to obtain enantioresolution of promethazine and trimeprazine. The estimated maximum and optimum resolution of trimeprazine and prometazine enantiomers (Rs = 1.74 and 2.01, respectively) corresponded to the following experimental conditions: pH 7.5; [HSA] 170 μM and plug length 190 s and pH 7.6; [HSA] 170 μM and plug length 170 s, for trimeprazine and prometazine, respectively. The developed methodologies were applied for the enantiomeric quality control of promethazine and trimeprazine enantiomers in commercially available pharmaceutical formulations. Resolution, accuracy, reproducibility, cost and sample throughput of the proposed methodologies make it suitable for quality control of the enantiomeric composition of promethazine and trimeprazine in pharmaceutical preparations.     

Thermoanalytical methods in vulcanizete analysis. Differential scanning calorimetry. Observations on the vulcanization process

Differential scanning calorimetry was used to follow the unaccelerated and accelerated sulfur vulcanization process in natural rubber and polybutadiene compounds. It was established that in both hard and soft rubber vulcanization, the heat of vulcanization (ΔH_v) depends only on the sulfur concentration provided other ingredients (carbon black, zinc oxide, stearic acid) and the elastomer blend ratio remain constant. Organic accelerators alter the temperature dependence of the exotherm but have no effect on ΔH_v over a considerable concentration range.The DSC exotherm was used to determine variations in sulfur/accelerator concentrations in production compounds. Analysis time is short—approx. 5 min—and a routine quality control method is suggested.     

Sequential injection spectrophotometric determination of phenylephrine hydrochloride in pharmaceutical preparations

A fully automated sequential injection spectrophotometric method for the determination of phenylephrine hydrochloride in pharmaceutical preparations is reported. The method is based on the condensation reaction of the analyte with 4-aminoantipyrine in the presence of potassium ferricyanide. The absorbance of the condensation product was monitored at 503 nm. A linear relationship between the relative peak height and concentration was obtained in the range 0.5-17.5 mg l⁻¹. The detection limit (as 3σ value) was 0.09 mg l⁻¹ and repeatability was 0.8 and 0.6% at 2.5 and 5 mg l⁻¹, respectively. Results obtained by this method agreed very well with those obtained by the AOAC official method.     

Thermoanalytical investigation of tin and cerium salt mixtures

Summary Oxide materials belonging to the Sn-Ce-O system are very interesting due to their use as solid electrolytes in fuel cells, catalysts, sensors and photoanodes in solar cells. The aim of the present work is to investigate the thermal behaviour of some tin and cerium salt mixtures. Mixtures with different representative Sn:Ce atomic ratio were prepared by classical ceramic method using SnC₂O₄, Ce(SO₄)₂·4H₂O and (NH₄)₂Ce(NO₃)₆ as starting compounds. The samples were investigated by means of TG/DTA methods in flowing and static air atmosphere. SnO₂ and/or CeO₂ were identified by X-ray diffraction and IR spectroscopy in the final decomposition products, depending on the initial composition of the both series. A different crystallinity degree of the solid products was observed depending on the Ce precursor.     

Comparison of analytical methods for quality control of pharmaceutical formulations containing glutathione

Summary The aim of this investigation was the study and development of analytical procedures suitable for the assay of glutathione (GSH) in pharmaceutical formulations. Two are based on isocratic HPLC with a 250 mm×4.6 mm i.d., 5 μm C₁₈ column and UV detection. In the first procedure sample solutions were injected without pretreatment whereas in the second the samples were injected after derivatization with Ellman’s reagent which forms an easily detectable adduct with GSH. Good linearity was obtained over the range 0.12–6.00×10⁻⁴M for the direct procedure and 0.25–3.00×10⁻⁴M for the derivatization procedure. The precision and rapidity of analysis were also good for both methods. The third method is based on capillary zone electrophoresis (CZE) in a 27 cm×75 μm i.d untreated fused silica capillary containing pH 7 phosphate buffer. All results are in good agreement with a spectrophotometric procedure used as reference method.     

Thermal stability of anti-rheumatic pharmaceutical drugs parecoxib sodium and valdecoxib

Thermal analysis of antirheumatic drugs, parecoxib sodium (PCX) and valdecoxib (VCX) was achieved. Thermogravimetry (TG), derivative thermogravimetry (DTG), and differential thermal analysis (DTA) were used through the work. The results led to thermal stability data, and also to the determination of kinetic parameters such as activation energy and frequency factor. The differential scanning calorimetry (DSC) was suitable for the purity determination of the compounds. The simplicity, speed, and low operational costs of thermal analysis justify its application in the quality control of pharmaceutical drugs.     

Thermoanalytical methods in the study of structure/properties relationships of modified and crosslinked linear polyethylene

Linear polyethylene is a typical semicrystalline polymer. Its physical and mechanical properties are strongly dependent on the crystallinity (crystalline fraction), and on the size and structure of the crystallites.Modification of linear polyethylene by the grafting of alkoxysilane groups and by subsequent network formation influences the crystalline properties of the polymer. DSC is eminently suitable to follow these changes. For crosslinked polyethylenes above the crystalline melting point, the modulus of elasticity and the thermal expansion coefficient determined by TMA give useful information on the structure. Comparison of the mechanical properties of grafted and crosslinked samples as a function of the crystallinity allows the separation of structural effects. A close correlation has been found between the structure and properties of modified and subsequently crosslinked polyethylenes.

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Zusammenfassung Lineares Polyethylen ist ein charakteristisch semikristallines Polymer. Seine physikalischen und mechanischen Eigenschaften hÄngen sehr stark von der KristallinitÄt (kristallinen Fraktion) und von der Grö\e und Struktur der Krsitallite ab. Eine Modifizierung linearen Polyethylenes durch Propfung von Alkoxysilangruppen und anschlie\ende Vernetzung beeinflu\t die Kristalleigenschaften des Polymers. Zu einer Untersuchung dieser VerÄnderungen ist DSC Äu\erst gut geeignet. Der mittels TMA ermittelte ElastizitÄtsmodul und WÄrmeausdehnungskoeffizient liefern bei vernetzten Polyethylenen über dem kristallinen Schmelzpunkt nützliche Informationen zur Struktur. Ein Vergleich der mechanischen Eigenschaften modifizierter und vernetzter Proben als Punktion der KristallinitÄt erlaubt die Herausstellung struktureller Einflüsse. Zwischen Eigenschaften und der Struktur von modifizierten und anschlie\end vernetzten Poly-ethylenen konnte eine enge Korrelation festgestellt werden.

     

外消旋化合物生物催化去对称化研究进展

手性化合物外消旋体的生物催化去对称化是目前生物与有机合成领域的重点、难点和热点,也是制备光学纯手性化合物的重要途径.我们将近年来发展起来的手性化合物生物催化去对称化的方法归纳为立体转化去对称化法、线性去对称化法、循环去对称化法、对映体收敛去对称化法和一步去对称化法5大类,对这些方法的原理、特点及其应用进展分别进行介绍,...     

Adsorption of naproxen enantiomers on chemically modified cellulose

Adsorption of naproxen enantiomers on the Chiralcel OJ-H chiral stationary phase, being tris(4-methylbenzoate) cellulose coated on silica gel, was studied. The thermodynamic characteristics of adsorption were measured. The adsorption isotherms are described by the Langmuir equation within the concentration range under study. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2303–2306, December, 2007.     

直链淀粉-三[(S)-1-苯乙基氨基甲酸酯]手性固定相拆分布地奈德对映体及其制剂含量的测定

22R-布地奈德的药物活性比22S-布地奈德的强2~3倍,开发布地奈德对映体拆分和定量分析方法,可为其药物研发及质量控制提供重要依据。目前,主要以反相C₁₈固定相对布地奈德对映体进行拆分,而采用手性固定相对其进行拆分少有报道。通过考察固定相、流动相和柱温对布地奈德对映体拆分的影响,建立了基于直链淀粉-三[(S)-1-苯乙基氨基甲酸酯]手性固定相快速拆分和检测布地奈德对映体的高效液相色谱方法,其色谱条件如下:色谱柱为Chiralpak AS-RH色谱柱(150 mm×4.6 mm, 5.0 μm),流动相为乙腈-水(45∶55, v/v),柱温40 ℃,流速1.0 mL/min,二极管阵列检测器(DAD),检测波长246 nm,进样量10 μL。在该色谱条件下,布地奈德的两个对映体得到较好拆分,22R-布地奈德和22S-布地奈德的保留时间分别6.40 min和7.77 min,分离度为4.64; 22R-布地奈德和22S-布地奈德分别在各自范围内线性关系良好,相关系数(R²)均为0.9999,检出限分别为0.05 μg/mL和0.07 μg/mL,定量限分别为0.16 μg/mL和0.20 μg/mL; 4个添加水平的样品加标回收率为102.63%~104.17%,相对标准偏差(RSD)为0.08%~0.57%(n=6)。将该方法应用于1批次4个吸入用布地奈德混悬液实际样品进行检测,22R-布地奈德和22S-布地奈德的含量分别为283.15~284.63 μg/mL和259.86~261.51 μg/mL。该方法操作简便,分析时间短,重复性好,准确度高,可用于布地奈德对映体的拆分及其制剂的质量控制。     

Four spectrophotometric methods for determination of nitrofurazone in pharmaceutical formulations

Four simple and sensitive visible spectrophotometric methods (A-D) for the determination of nitrofurazone in bulk samples and pharmaceutical formulations are described. They are based on the formation of colored species by treating either its reduction product with 3-methylbenzothiazolin-2-one hydrazone in the presence of ferric chloride (method A: _max 600 nm) or its hydrolysis product with thiobarbituric acid (method B: _max 520 nm, 440 nm) or barbituric acid (method C: _max 400 nm) or by oxidizing it with excess N-bromosuccinimide and determining the consumed NBS using metol-isonicotinic acid hydrazide (method D: _max 620 nm).     

Optimization of sample preparation using statistical methods: spectrophotometric determination of Fe and Co in pharmaceutical samples

This work presents alternatives for Fe and Co determination in pharmaceutical samples using flow analysis. The first procedure describes Fe extraction in mineral/vitamin complexes. The best conditions were reached when HNO₃ concentration and volume, sample mass and shaking time were 1.0 mol l⁻¹, 5 ml, 25 mg and 10 min. Three mineral/vitamin complexes of known concentrations (ranging from 12 to 32 g kg⁻¹) were analyzed (10 authentic replicates for each) and recoveries of around 100% were obtained when compared with a well-established mineralization procedure employing concentrated HNO₃ and H₂O₂ (30% w/v). The second work part shows the employment of Tiron and H₂O₂ reaction for Co determination in a drug for inappetence. The results (352±18.7 mg kg⁻¹) were compared with those using Electrothermal Atomic Absorption Spectrometry—ETAAS (346±15.7 mg kg⁻¹). The proposed method showed detection and quantification limits of 0.20 and 0.70 μg l⁻¹, respectively. Both procedures for Fe and Co determination presented time, reagent and effort reduction.